JP5935584B2 - Method for producing adamantanecarboxylic acid glycidyl ester compound - Google Patents

Description

  The present invention is excellent in optical properties, heat resistance, etc., for semiconductor encapsulants, cross-linked resins, optical materials such as optical fibers and optical waveguides, optical disk substrates, raw materials thereof, pharmaceutical / agrochemical intermediates, and other various industrial products. The present invention relates to a method for producing a suitable adamantanecarboxylic acid glycidyl ester compound.

  Since adamantane has a rigid structure, transparency, heat resistance, and high refractive index, and its derivatives exhibit unique functions, high-performance resin materials (Patent Document 1), pharmaceutical intermediates, optical materials, It is known to be useful for a photoresist or the like.

  In patent document 1, the hardened | cured material which consists of epoxy compounds, such as adamantane dicarboxylic acid and bisphenol A diglycidyl ether, is disclosed as a heat resistant epoxy resin hardened | cured material.

  In Patent Document 2, a copolymer containing an adamantane ester as a structural unit is disclosed as an optical resin excellent in heat resistance and optical characteristics that can be used as a fiber material for optical transmission and the like, and is a raw material thereof. A method for producing adamantanedicarboxylic acid glycidyl ester is disclosed.

  Thus, the epoxy resin hardened material containing an adamantane skeleton is expected to have excellent properties as a highly functional resin material. However, an adamantanecarboxylic acid glycidyl ester compound as a raw material has not yet been developed as a production method that is satisfactory in terms of yield and handling. Patent Document 2 discloses a production example of diglycidyl adamantanedicarboxylate, but the disclosed production example has a low yield and is not yet industrially satisfactory. Non-Patent Document 1 discloses a method for producing glycidyl adamantanecarboxylate as an epoxy resin raw material. However, the disclosed production method requires adamantanecarboxylic acid sodium salt as a starting material, and if the sodium salt is not commercially available, it must be prepared separately. Furthermore, there was a problem that water was easily mixed into the reaction system due to inadequate preparation or moisture absorption, and a by-product was easily generated.

JP 55-115423 A JP 2003-321530 A

Journal of General Chemistry USSR, 60, 2725 (1990)

  An object of the present invention is to provide a method for producing an industrially useful adamantanecarboxylic acid glycidyl ester compound in a simple and high yield.

As a result of intensive studies on the above problems, the present inventors reacted an adamantanecarboxylic acid compound with epichlorohydrin and / or epibromohydrin to produce an adamantanecarboxylic acid glycidyl ester compound. It was found that the desired product can be obtained simply and in high yield by coexisting a specific organic amine, and the present invention has been completed.
That is, in the present invention, an adamantanecarboxylic acid compound represented by the general formula (I) is mixed with epichlorohydrin and / or epibromohydrin (hereinafter referred to as epichloro (bromo) hydrin) When an adamantanecarboxylic acid glycidyl ester compound represented by the formula (II) is produced, at least one amidine compound represented by the general formula (III) is allowed to coexist, It is a manufacturing method.

（式中、Ｒ^１はそれぞれ独立に、炭素数１〜１０のアルキル基、アリール基、シクロアルキル基、炭素数１〜１０のアルコキシ基、アリールオキシ基、炭素数２〜６のアシルオキシ基、ハロゲン基を示し、ｍは０〜３、カルボキシル基は橋頭位炭素に結合し、ｎは１〜３の整数を示す）

(In the formula, each R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group, an acyloxy group having 2 to 6 carbon atoms, or a halogen. A group, m is 0 to 3, a carboxyl group is bonded to a bridgehead carbon, and n is an integer of 1 to 3)

（式中、Ｒ^１、ｍ及びｎは一般式（Ｉ）と同じ。）

(In the formula, R ¹ , m and n are the same as those in the general formula (I).)

（式中、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５、はそれぞれ独立に、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基を示し、Ｒ^２とＲ^４は結合して環構造を形成しても良く、Ｒ^３とＲ^５は結合して環構造を形成して良い。）

(In the formula, R ² , R ³ , R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and R ² and R ⁴ are bonded to each other. A ring structure may be formed, and R ³ and R ⁵ may be bonded to form a ring structure.)

  Industrial Applicability According to the present invention, as an optical resin material excellent in heat resistance and optical characteristics, which can be used for semiconductor sealing materials, optical transmission fiber materials, optical waveguides, optical disk substrates, cross-linked resins, etc., industrially Provided is a simple method for producing a useful adamantanecarboxylic acid glycidyl ester compound in high yield.

2 is a graph showing a ¹ H-NMR spectrum of a white solid finally obtained in Example 1. FIG. 2 is a graph showing a ¹³ C-NMR spectrum of a white solid finally obtained in Example 1. FIG. 4 is a graph showing a ¹ H-NMR spectrum of a white solid finally obtained in Example 4. 6 is a graph showing a ¹³ C-NMR spectrum of a white solid finally obtained in Example 4. 6 is a graph showing a ¹ H-NMR spectrum of a white solid finally obtained in Example 5. FIG. 6 is a graph showing a ¹³ C-NMR spectrum of a white solid finally obtained in Example 5. FIG.

  Hereinafter, the present invention will be described in more detail. The adamantanecarboxylic acid compound used in the present invention is represented by the general formula (I). It is characterized in that 1 to 3 carboxyl groups are bonded to the bridgehead carbon of the adamantane skeleton. Specifically, 1-adamantane carboxylic acid, 1,3-adamantane dicarboxylic acid, 1,3,5-adamantane tricarboxylic acid, 3-methyl-1-adamantane carboxylic acid, 3-ethyl-1-adamantane carboxylic acid, 5 -Methyl-1,3-adamantane dicarboxylic acid, 5-ethyl-1,3-adamantane dicarboxylic acid, 5,7-dimethyl-1,3-adamantane dicarboxylic acid, 3-bromo-1-adamantane carboxylic acid, 5-bromo -1,3-adamantane dicarboxylic acid, 3-methoxy-1-adamantane carboxylic acid, 3-ethoxy-1-adamantane carboxylic acid, 3-propoxy-1-adamantane carboxylic acid, 3-butoxy-1-adamantane carboxylic acid, etc. Can be mentioned.

  In the present invention, both epichlorohydrin and epibromohydrin can be suitably used. The amount of epibromohydrin is 1 to 20 equivalents, preferably 2 to 10 equivalents, more preferably 3 to 7 equivalents with respect to the carboxy group of the adamantanecarboxylic acid compound represented by the general formula (I). If it is 1 equivalent or more, it will become difficult to produce by-products such as dimers. Less than 20 equivalents is preferable because it is economical and requires less labor for the purification process. Epichlorohydrin is inferior in reactivity to epibromohydrin, so it should be added in a large amount. The amount of epichlorohydrin to be added is 1 to 100 equivalents, preferably 5 to 50 equivalents, more preferably 10 to 30 equivalents with respect to the carboxy group of the adamantanecarboxylic acid compound represented by the general formula (I). is there. In addition, after the reaction is completed, epichloro (bromo) hydrin recovered from a purification process such as vacuum distillation can be reused.

  The amidine compound represented by the general formula (III) used in the present invention is specifically 1,8-diazabicyclo [5.4.0] undec-7-ene represented by the general formula (IV), 1,5-diazabicyclo [4.3.0] non-5-ene represented by (V). The amount of the amidine compound to be added is 0.1 to 10.0 equivalents, preferably 0.5 to 5.0 equivalents, more preferably relative to the carboxy group of the adamantanecarboxylic acid compound represented by the general formula (I). Is 0.8 to 3.0 equivalents. If it is 0.1 equivalent or more, it is difficult to produce a by-product containing halogen and the yield is improved, and if the amount used is 10.0 equivalent or less, it is economically preferable.

  An adamantanecarboxylic acid compound represented by the general formula (II) is reacted with an epichloro (bromo) hydrin in the presence of an amidine compound represented by the general formula (III). In the method for producing a glycidyl ester compound, there is no limitation on the order of mixing each. For example, after mixing an adamantanecarboxylic acid compound and epichloro (bromo) hydrin in a reaction solvent, an amidine compound may be added, or after mixing an adamantanecarboxylic acid compound and an amidine compound, Epichloro (bromo) hydrin may be added, or after mixing epichloro (bromo) hydrin and amidine compound, an adamantanecarboxylic acid compound may be added. When adding, it may be added as it is, or may be diluted with a part of the reaction solvent. Among them, the mixing order in which the adamantanecarboxylic acid compound and amidine compound are first mixed in the reaction solvent and then added to epichloro (bromo) hydrin makes it easy to control the rise in liquid temperature, and the adamantanecarboxylic acid compound However, it is preferable because the handling operation as a solution becomes simple and the progress of the side reaction is suppressed.

  The reaction solvent in the present invention is preferably an aprotic polar solvent such as acetonitrile, benzonitrile, nitrobenzene, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, 2,6-lutidine, hexamethylphosphoric triamide, It can also be carried out with a hydrophobic solvent such as chloroform. Furthermore, although it can be carried out without a solvent, it is desirable to use a solvent from the viewpoint of easy handling and reaction control. Among them, acetonitrile is preferable because it sufficiently dissolves the substrate and has a high reaction selectivity. These solvents can be used alone or in a system in which two or more solvents are mixed. The amount of solvent is 0.1-100 mass parts with respect to 1 mass part of adamantanecarboxylic acid compounds, Preferably it is used in the ratio of 1-20 mass parts.

  In the case of using a solvent, if a large amount of water is contained in the solvent, a water addition reaction to the epoxy ring occurs and the selectivity is lowered. Therefore, it is desirable to use after dehydrating the solvent with molecular sieves or the like. . The water content in the solvent is preferably 5% by mass or less, preferably 1% by mass or less, and more preferably 0.5% by mass because the selectivity is improved.

  The reaction temperature is −78 to 150 ° C., preferably −20 to 100 ° C., more preferably about −10 to 60 ° C. Within this range, the glycidyl esterification of the carboxy group proceeds sufficiently and the side reaction proceeds little. The reaction time is 0.5 to 1000 hours, preferably 1 to 100 hours. Since the reaction time depends on the reaction temperature and the amount of solvent, it is not limited to the above range. In addition, the reaction pressure is not particularly limited, and the reaction can be performed at normal pressure or under pressure.

After completion of the reaction, the target adamantanecarboxylic acid glycidyl ester compound represented by the general formula (II) is purified from the reaction solution. The purification method is not particularly limited, but the following method can provide a product having a high yield of adamantanecarboxylic acid glycidyl ester compound and less impurities.
(I) After completion of the reaction, a hydrophobic solvent such as chloroform and in which the target adamantanecarboxylic acid glycidyl ester compound is dissolved is added to the reaction solution and washed with pure water.
(Ii) The organic layer after washing is concentrated, and the coloring components are removed with a silica gel column, activated carbon, activated alumina or the like.
(Iii) The collected solution is concentrated in vacuo under a nitrogen stream.

  In this production method, when n is 2 or 3 in the general formula (II), a by-product (general formula (VI) in which partial glycidyl esterification does not proceed, halide ions or water present in the system) In some cases, a by-product (general formula (VII)) and a multimerization by-product (general formula VIII) are included.

（式中、Ｒ^１、ｍ及びｎは一般式（Ｉ）と同じ。ａは１又は２を示し、ａ＜ｎである。）

(In the formula, R ¹ , m and n are the same as those in formula (I). A represents 1 or 2, and a <n.)

（式中、Ｒ^１、ｍ及びｎは一般式（Ｉ）と同じ。Ｘは水酸基、塩素又は臭素を示し、ｂは２又は３を示し、ｂ≦ｎである。）

(In the formula, R ¹ , m and n are the same as those in the general formula (I). X represents a hydroxyl group, chlorine or bromine, b represents 2 or 3, and b ≦ n.)

（式中、Ｒ^１、ｍ及びｎは一般式（Ｉ）と同じ。）

(In the formula, R ¹ , m and n are the same as those in the general formula (I).)

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all to a following example.

Example 1
<Production of 1,3-adamantanedicarboxylate diglycidyl>
In a 1 L jacketed separable three-necked flask equipped with a stirrer and a thermometer, 22.41 g (0.10 mol) of 1,3-adamantanedicarboxylic acid, 1,8-diazabicyclo [5.4.0] undec-7-ene 48 .71 g (0.32 mol), epibromohydrin 109.58 g (0.8 mol), and acetonitrile 100 ml were charged and stirred at 20 ° C. for 2 hours. After completion of the reaction, 200 ml of chloroform was added, and a washing operation using 200 ml of ion exchange water was performed three times, and a washing operation using a 0.5% aqueous sodium sulfate solution was performed three times. After adding 10 g of sodium sulfate and dehydrating and filtering through 5C filter paper, the solvent was distilled off under reduced pressure. The resulting viscous liquid was fractionated and purified by silica gel column chromatography (chloroform: methanol = 98/2, Rf = 0.4). Concentration under a nitrogen stream under the conditions of 2 mmHg and 100 ° C. gave 26.94 g of the intended product as a pale yellow viscous liquid (yield 80%). ^The structure was confirmed by ¹ H and ¹³ C-NMR (see Charts 1 and 2). ¹ H-NMR spectrum: δ 1.6-2.2 ppm (14H, adamantane), 2.6 ppm, 2,8 ppm (4H, glycidyl group 3-position), 3.2 ppm (2H, glycidyl 2-position), 3.9 ppm, 4.4 ppm (4H, glycidyl 1st position). ¹³ C-NMR spectrum: 27 to 41 ppm (adamantane), 44 ppm (glycidyl group 3-position), 49 ppm (glycidyl group 2-position), 64 ppm (glycidyl group 1-position), 176 ppm (carbonyl).

Example 2
<Production of 1,3-adamantanedicarboxylate diglycidyl>
To a 300 ml three-necked flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 11.21 g (0.05 mol) of 1,3-adamantanedicarboxylic acid, 1,8-diazabicyclo [5.4.0] undec-7-ene 27.40 g (0.18 mol), epichlorohydrin 148.03 g (1.6 mol), 50 ml of acetonitrile were charged, and the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, 200 ml of chloroform was added, and a washing operation using 200 ml of ion exchange water was performed three times, and a washing operation using a 0.5% aqueous sodium sulfate solution was performed three times. After adding 10 g of sodium sulfate and dehydrating and filtering through 5C filter paper, the solvent was distilled off under reduced pressure. The resulting viscous liquid was fractionated and purified by silica gel column chromatography (chloroform: methanol = 98/2, Rf = 0.4). The mixture was concentrated under conditions of 2 mmHg and 100 ° C. under a nitrogen stream to obtain 12.62 g as a pale yellow viscous liquid (yield 75%). ^The structure was confirmed by ¹ H and ¹³ C-NMR.

Example 3
<Production of 1,3-adamantanedicarboxylate diglycidyl>
In a 1 L jacketed separable three-necked flask equipped with a stirrer and a thermometer, 11.21 g (0.05 mol) of 1,3-adamantanedicarboxylic acid, 1,5-diazabicyclo [4.3.0] non-5-ene 21 .11 g (0.17 mol), epibromohydrin 54.80 g (0.4 mol), and acetonitrile 100 ml were charged and stirred at 30 ° C. for 2 hours. After completion of the reaction, 200 ml of chloroform was added, and a washing operation using 200 ml of ion exchange water was performed twice, and a washing operation using a 0.5% aqueous sodium sulfate solution was performed twice. After adding 10 g of sodium sulfate and dehydrating and filtering through 5C filter paper, the solvent was distilled off under reduced pressure. The resulting viscous liquid was fractionated and purified by silica gel column chromatography (chloroform: methanol = 98/2, Rf = 0.4). Concentration was performed under conditions of 2 mmHg and 100 ° C. to obtain 12.29 g as a pale yellow viscous liquid (yield 73%). ^The structure was confirmed by ¹ H and ¹³ C-NMR.

Example 4
<Production of triglycidyl 1,3,5-adamantane tricarboxylate>
In a 1 L jacketed separable three-necked flask equipped with a stirrer and a thermometer, 13.41 g (0.05 mol) of 1,3,5-adamantanetricarboxylic acid, 1,8-diazabicyclo [5.4.0] undec-7- 36.54 g (0.24 mol) of ene, 82.20 g (0.6 mol) of epibromohydrin and 100 ml of acetonitrile were charged and stirred at 30 ° C. for 2 hours. After completion of the reaction, 200 ml of chloroform was added, and washing operation using 200 ml of ion-exchanged water was performed three times. After adding 10 g of sodium sulfate and dehydrating and filtering through 5C filter paper, the solvent was distilled off under reduced pressure. The resulting viscous liquid was fractionated and purified by silica gel column chromatography (chloroform: ethyl acetate = 15/1, Rf = 0.2). Concentration was carried out under conditions of 2 mmHg and 100 ° C. to obtain 11.3 g as a pale yellow viscous liquid (yield 52%). ^The structure was confirmed by ¹ H and ¹³ C-NMR (see charts 3 to 4). ¹ H-NMR spectrum: δ 1.7 to 2.3 ppm (13H, adamantane), 2.6 ppm, 2,8 ppm (6H, glycidyl group 3-position), 3.2 ppm (3H, glycidyl 2-position), 3.9 ppm, 4.4 ppm (6H, glycidyl 1st position). ¹³ C-NMR spectrum: 27 to 41 ppm (adamantane), 44 ppm (glycidyl group 3-position), 49 ppm (glycidyl group 2-position), 65 ppm (glycidyl group 1-position), 175 ppm (carbonyl).

Example 5
<Production of diglycidyl 5,7-dimethyl-1,3-adamantane dicarboxylate>
In a 1 L jacketed separable three-necked flask equipped with a stirrer and a thermometer, 12.62 g (0.05 mol) of 5,7-dimethyl-1,3-adamantanedicarboxylic acid, 1,8-diazabicyclo [5.4.0] Undeca-7-ene 27.40 g (0.18 mol), epibromohydrin 54.80 g (0.4 mol), 50 ml of acetonitrile were charged, and the mixture was stirred at 20 ° C. for 5 hours. After completion of the reaction, 200 ml of chloroform was added, and washing operation using 200 ml of ion-exchanged water was performed three times. After adding 10 g of sodium sulfate and dehydrating and filtering through 5C filter paper, the solvent was distilled off under reduced pressure. The resulting viscous liquid was fractionated and purified by silica gel column chromatography (hexane / ethyl acetate = 5/2, Rf = 0.4). Concentration under conditions of 2 mmHg and 100 ° C. gave 14.87 g of the target product as a pale yellow viscous liquid (yield 82%). ^The structure was confirmed by ¹ H and ¹³ C-NMR (see charts 5 to 6). ¹ H-NMR spectrum: δ 0.9 ppm (6H, methyl group), 1.1 to 1.9 ppm (12H, adamantane), 2.6, 2.8 ppm (4H, glycidyl group 3-position), 3.2 ppm (2H Glycidyl 2-position), 3.9 ppm, 4.4 ppm (4H, glycidyl 1-position). ¹³ C-NMR spectrum: 30 ppm (methyl group) 31 to 44 ppm, 49 ppm (adamantane), 44 ppm (glycidyl group 3-position), 49 ppm (glycidyl group 2-position), 64 ppm (glycidyl group 1-position), 176 ppm (carbonyl).

Comparative Example 1
In a 300 L three-necked flask equipped with a stirrer and a thermometer, 11.21 g (0.05 mol) of 1,3-adamantanedicarboxylic acid, 12.65 g (0.16 mol) of pyridine, 54.80 g of epibromohydrin (0.40 mol) ), Charged with 100 ml of acetonitrile, stirred at 50 ° C., and monitored the reaction by HPLC over time. After 6 hours from the start of the reaction, no increase was confirmed after the reaction yield of the target product reached 24%.

Comparative Example 2
The same procedure as in Comparative Example 1 was performed except that the amount of pyridine added was changed to 7.91 g (0.10 mol). After 6 hours from the start of the reaction, no increase was confirmed after the reaction yield of the target product reached 22%.

Comparative Example 3
In a 300 L three-necked flask equipped with a stirrer and a thermometer, 11.21 g (0.05 mol) of 1,3-adamantanedicarboxylic acid and 12.34 g (0.11 mol) of potassium t-butoxide were mixed in 100 ml of acetonitrile. Bromohydrin (54.80 g, 0.40 mol) was added to a solution of acetonitrile in 100 ml, stirred at 25 ° C., and the reaction was monitored by HPLC over time. Although confirmed for 18 hours from the start of the reaction, the formation of the target product was not confirmed.

Claims (9)

An adamantanecarboxylic acid glycidyl ester compound represented by the general formula (II) is produced by reacting an adamantanecarboxylic acid compound represented by the general formula (I) with epichlorohydrin and / or epibromohydrin. In the method, a method for producing an adamantanecarboxylic acid glycidyl ester compound in which at least one amidine compound represented by the general formula (III) coexists and the reaction temperature is in the range of −10 to 60 ° C.

(In the formula, each R1 is independently an alkyl group having 1 to 10 carbon atoms, an aryl group, a cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group, an acyloxy group having 2 to 6 carbon atoms, or a halogen group. M represents 0 to 3, the carboxyl group is bonded to the bridgehead carbon, and n represents an integer of 1 to 3)

(In the formula, R1, m and n are the same as those in the general formula (I).)

(In the formula, R2, R3, R4 and R5 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and R2 and R4 are bonded to form a ring structure. R3 and R5 may be bonded to form a ring structure.) The method for producing an adamantanecarboxylic acid glycidyl ester compound according to claim 1, wherein the amidine compound represented by the general formula (III) is a compound represented by the general formula (IV) or the general formula (V).

  The adamantanecarboxylic acid according to claim 1 or 2, wherein the amidine compound represented by the general formula (III) is used in an amount of 0.1 to 10.0 equivalents relative to the carboxyl group of the adamantanecarboxylic acid compound represented by the general formula (I). A method for producing an acid glycidyl ester compound.   The production of an adamantanecarboxylic acid glycidyl ester compound according to any one of claims 1 to 3, wherein epibromohydrin is used in an amount of 1 to 20 equivalents relative to a carboxyl group of the adamantanecarboxylic acid compound represented by the general formula (I). Method.   The production of an adamantanecarboxylic acid glycidyl ester compound according to any one of claims 1 to 4, wherein epichlorohydrin is used in an amount of 1 to 100 equivalents based on the carboxyl group of the adamantanecarboxylic acid compound represented by the general formula (I). Method. Use one or more reaction solvents from the group consisting of acetonitrile, benzonitrile, nitrobenzene, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, 2,6-lutidine, hexamethylphosphoric triamide, chloroform, Item 6. A method for producing an adamantanecarboxylic acid glycidyl ester compound according to any one of Items 1 to 5 .   The method for producing an adamantanecarboxylic acid glycidyl ester compound according to any one of claims 1 to 6, wherein the adamantanecarboxylic acid glycidyl ester compound represented by the general formula (II) is 1,3-adamantane dicarboxylic acid diglycidyl compound. The method for producing an adamantanecarboxylic acid glycidyl ester compound according to any one of claims 1 to 6 , wherein the adamantanecarboxylic acid glycidyl ester compound represented by the general formula (II) is 1,3,5-adamantanetricarboxylic acid triglycidyl compound. . The adamantanecarboxylic acid glycidyl ester compound according to any one of claims 1 to 6 , wherein the adamantanecarboxylic acid glycidyl ester compound represented by the general formula (II) is 5,7-dimethyl-1,3-adamantanedicarboxylic acid diglycidyl compound. Manufacturing method.

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